JPS6155178A - Release agent - Google Patents

Abstract

PURPOSE:A release agent capable of forming a feelable film which is easily peelable and can be excellently written when applied on the surface of a base material (the surface to be treated), containing a specified alkylene oxide polymer having reactive silicon functional groups. CONSTITUTION:A release agent containing an alkylene oxide polymer (molecular weight: 300-30,000) which consists of a principal chain constituted of the repeating units of formula I [where R<1> is a 1-8C divalent hydrocarbon group (e.g., a group of formula II)] and contains at least one reactive silicon functional group (e.g., a hydrolyzable silicon-containing group attached to an Si atom). This release agent is especially useful as a treating agent for the back surface of a kraft tape for packaging one surface of which has been coated with a rubber self-adhesive.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is used for back surface treatment of adhesive products such as pressure-sensitive adhesive tapes and adhesive sheets, and for surface treatment of release paper and release films. The present invention relates to a release treatment agent.

[Prior Art] Conventionally, release agents used for purposes such as back treatment of adhesive products and surface treatment of release papers and release films include polysiloxane compounds, acrylic acid compounds having long chain alkyl groups, and polyesters. Peeling agents using polymeric compounds such as polyamide-based and polyamide-based are often used.

The performance required of these release agents is that when used, they must have good peelability from the adhesive, have a durable peeling effect, and have no adverse effect on the adhesive performance. The material must have good adhesion to the substrate, heat resistance, writability, and printability, and it must also be easy to process.

Those using a release agent using a polysiloxane compound have good releasability, but have no writability, so they have the disadvantage that it is difficult to write on them. In addition, products using polymeric compounds such as acrylic acid, polyester, and polyamide that have long-chain alkyl groups have writing properties, but have poor removability. It is unsuitable as a drug.

[Problems to be Solved by the Invention] The present invention provides a polysiloxane compound containing a polysiloxane compound with good releasability. There is a disadvantage that the writability is poor when using a processing agent, or when a release agent containing a high molecular compound such as an acrylic acid type, polyester type, or polyamide type that has a long chain alkyl group and has good writability is used. This product was developed to overcome the disadvantages of kraft paper adhesive tape, which has poor removability and is unsuitable as a backing agent for low-strength kraft paper adhesive tapes. Excellent peeling! This was done in order to find a peeling agent that has Il female properties.

Means for Solving Problems] The present invention provides that the main chain essentially has the general formula: % formula % (wherein R1 represents a divalent hydrocarbon group having 1 to 8 carbon atoms). Molecular group 3 consisting of the repeating units shown and having at least one reactive silicon functional group in the molecule
The present invention relates to a release agent characterized in that it contains an alkylene oxide polymer having a molecular weight of 00 to 30,000.

[Example] In the present invention, an alkylene oxide polymer having a reactive silicone functional group is used to prepare a release agent.

The alkylene oxide polymer having a reactive silicone functional group used in the present invention means that the main chain essentially has the general formula: % formula % (wherein R1 is a divalent hydrocarbon group having 1 to 8 carbon atoms) For example, a polyether, ether-ester block copolymer, etc., consisting of a repeating unit represented by
~15,000 alkylene oxide polymer.

The main chain of the alkylene oxide polymer essentially has the general formula: -4 hydrocarbon groups, most preferably). Specific examples of R1 include -CHz-1-CH2C
H2~, -CCHz-1-CHz CH2CH2CH2
-CH3 and the like. The main chain of the alkylene oxide polymer may consist of only one type of alkylene oxide repeating unit, or it may consist of two or more types of repeating units, but R1 is particularly CHz -CHCH2- is preferred.

The above-mentioned reactive silicon functional group is, for example, a silicon-containing group having a hydrolyzable group bonded to a silicon atom or a silanol group. It refers to a group that causes a condensation reaction, and a typical example is a group represented by the general formula (1). R2 in the general formula (1) is a hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group represented by the general formula: %Formula%, and R' in the formula
is a hydrocarbon group having 11 to 20 carbon atoms, and specific examples include alkyl groups such as methyl group and ethyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group, and benzyl group. Examples include aralkyl groups, and the three R's may be the same or different. Also, X in general formula (1) is water 111! or a hydrolyzable group, and when two or more X's are included, they may be the same or different. a is 0.1.2 or 3, b is 0.1 or 2, I
ll is 0 or an integer from 1 to 18.

Specific examples of the hydrolyzable group represented by X in the general formula (1) include a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an aminooxy group, a mercapto group, and an alkenyl group. Examples include oxy groups. Among these groups, alkoxy groups are preferred because they are easy to handle. Furthermore, R2 is preferably a methyl group or a phenyl group from the viewpoint of easy availability of raw materials.

As a method for obtaining the alkylene oxide polymer having a reactive silicone functional group, for example,
No. 36319, No. 4 (No. 3-12154, No. 49-32)
No. 673, JP-A No. 5O-15G599, JP-A No. 51-73
No. 561, No. 54-(No. 3096, No. 55-137G)
No. 8, No. 55-82123, No. 55-123620, No. 55-125121, No. 55-131021,
Examples include methods proposed in Publications No. 55-131022, No. 55-135135, and No. 55-137129.

The alkylene oxide polymer having a reactive silicone functional group as described above is, for example, a hydrogenated silicon compound represented by the general formula (2J: (wherein R2, X% a 1.b and m are the same as above) , the general formula (3
): %Formula%(3) (In the formula, R3 is a hydrogen atom, a halogen atom, or a carbon number of 1
~20 substituted or non-monosubstituted monovalent aliphatic hydrocarbon groups, 2 is a divalent organic group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, C is O or 1) It can be produced by adding a hydrosilylation reaction to an alkylene oxide polymer having an unsaturated group using a platinum-based compound such as chloroplatinic acid as a catalyst, but it is not limited to this method. do not have.

Specific examples of hydrogenated silicon compounds represented by the general formula (21) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, and methyldimethoxysilane. , phenyldimethoxysilane, 1,3,3,5.S, 7
Alkoxysilanes such as ,7-hebutamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane: Bis(dimethylketoximate)methylsilane, bis(cyclo Ketoximate silanes such as xylketoximate) methylsilane, bis(diethylketoximate)trimethylsiloxysilane; dimethylsilane, trimethylsiloxymethylsilane,
Examples include hydrosilanes such as 1,1-dimethyl-2,2-dimethyldisiloxane; alkenyloxysilanes such as methyltri(isopropenyloxy)silane, but are not limited to these.

As a specific method for producing an alkylene oxide polymer having an unsaturated group represented by the general formula (3), JP-A-54-8
Unsaturation can be achieved in the side chain by the method disclosed in Publication No. 097 or by adding and copolymerizing an epoxy compound containing an unsaturated group such as allyl glycidyl ether when polymerizing an epoxy compound such as ethylene oxide or propylene oxide. Examples include methods of introducing groups.

R3 in the alkylene oxide polymer having an unsaturated group represented by general formula (3) is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom. 2 has 1 to 40 carbon atoms, preferably 1
~20 divalent organic groups, -R-1-ROR-1,000 -R-OC-1-RNHC-1-RC- (R is carbon@1
~20 divalent hydrocarbon groups, which may be the same or different if two R's are contained)
is preferable, and a methylene group is particularly preferable.

In the reaction between the hydrogenated silicon compound represented by the general formula (21) and the alkylene oxide polymer having an unsaturated group represented by the general formula (3), after reacting them, some or all of the It may also be converted into other hydrolyzable groups or hydroxyl groups.For example, if X is a halogen group or a hydride group, it may be converted into an alkoxy group,
It is preferable to use it after converting it into an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group, or the like.

A curing catalyst may be used when preparing the release agent of the present invention.

Such curing catalysts include tetrabutyl titanate,
Titanate esters such as tetrapropyl titanate, wired tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; tin octylate; butylamine, octylamine, dibutylamine, monoethanolamine , jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4. G-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,
1.3-diazabicyclo<5゜4.6) undecene-7
Amine compounds such as (OBtJ) or their salts such as carboxylic acids; Low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; Reaction products of excess polyamines and epoxy compounds; Silane coupling with amino groups agents, such as γ-aminopropyl trime
Commonly known silanol condensation catalysts such as toxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane can be mentioned. These may be used alone or in combination of two or more kinds.

In addition, in order to improve workability and reduce viscosity, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. , a ketone solvent such as diisobutyl ketone, etc. may be blended.

The release agent of the present invention may be used in combination with commonly used release agents in order to adjust physical properties. In that case, the commonly used stripping agent is
In the case of a release agent using a polysiloxane compound, a phenyl group-containing polysiloxane compound is used, and in the case of a release agent using a polymer compound having a long chain alkyl group, Acrylic acid-based agents are particularly preferred because they have good compatibility with the release agent of the present invention.

Additives may be used in the release agent of the present invention for the purpose of adjusting the hardness of the coating film, adhesion to the substrate, curing speed, pot life, etc.

Additives used for the above purpose include various silane coupling agents, such as alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenosilane; Alkylisopropenoxysilanes such as xysilane, methyltriisopropenoxysilane, γ-glycidoxybutylmethyldiisobrobenoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimeritoxysilane , vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-7 minobrobyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane Examples include alkoxysilanes having functional groups such as; silicone varnishes; polysiloxanes.

In addition, when using the above-mentioned other release treatment agents together or adding additives, the proportion of the alkylene oxide polymer having a reactive silicone functional group in the solid content of the release treatment agent is 1 to 95% ( It is preferably 5% to 90% by weight (the same applies hereinafter), and more preferably 5 to 90%.

The amount of the release treatment agent of the present invention to be applied to a film, paper, etc. varies depending on the base material, required release properties, etc., but is usually 0.5 to 1. A sufficient effect can be obtained with Og 7m 2.

There are no particular limitations on the base material, and any material that is generally used as a base material for release treatment agents, such as porcelain and films, can be used.

To illustrate the method of operating the release agent of the present invention, for example, preparing the release agent of the present invention as a 1.0% toluene solution,
It may be applied to a substrate using a coater or the like, and heat-treated at a temperature of about 90° C. for about 1 minute.

The back surface of the tape substrate, release paper, and release film treated in this manner can be used for various adhesive tapes such as rubber-based, acrylic-based, or silicone-based adhesive tapes. In particular, the release agent of the present invention has excellent release properties against rubber adhesives, has writing properties because it contains an alkylene oxide polymer whose main chain is essentially polyalkylene oxide, and It also has the advantage of not slipping easily when pasted on cardboard and stacked.

Therefore, it is particularly useful as a back treatment agent for packaging craft tape coated with a rubber adhesive.

Although it is not clear why products treated with the release treatment agent of the present invention exhibit releasability, one reason is believed to be the presence of silicon-containing groups contained in the alkylene oxide polymer.

In other words, since this silicon-containing group has reactivity, it creates crosslinks between the alkylene oxide polymers and has the function of increasing the adhesion to the substrate at the same time as polymerizing the polymer. This is thought to be due to the formation of polysiloxane bonds to form a network structure of the polyether-polysiloxane block polymer.

Another reason why the release treatment agent of the present invention has releasability is that
Particularly for rubber-based adhesives, it is important to note that the polyether main chain of the release agent of the present invention itself is not compatible with both the base rubber of the rubber-based adhesive and the tackifying resin used therein. can give.

Thus, the release agent of the present invention is a polymer having both a polyether main chain portion and a polysiloxane portion, and has both release performance and writability, and has pressure-sensitive adhesive properties. It is useful as a backside treatment agent for pressure-sensitive adhesive sheets, etc., and as a release treatment agent for release papers and release films.

Next, the release agent of the present invention will be explained with reference to Examples.

In addition, each physical property value was measured by the following method.

(Peeling force) Width 2Si made by laminating adhesive tape and release treatment film
A tape-shaped sample piece of llu was peeled off at a peeling rate of 30On+n+/
Measure the load after peeling off the adhesive tape and release film in a 180 degree direction.

(Relative Peeling Force) The relative value of the above peeling force when the adhesive force to the stainless steel plate is 100 is shown as the relative peeling force.

(Tack) J Is Z 0237-1980 Ni Semi-L; TJ, D
Measured using the OW rolling ball tack method (30 degree tilt angle).

(Adhesive strength) In accordance with Jl 3 Z 0237-1980, adhesive tape was attached to a stainless steel plate with a width of 25 mm by moving a 2ka rubber roll back and forth twice, and then peeled at a peeling speed of 300 m.
Measure the load when peeling in the 180 degree direction in mZ minutes.

(Residual adhesion rate) Among the adhesive forces to the stainless steel plate, the relative value when the adhesive force before aging is taken as 100 is shown as the residual adhesion rate.

Production Example 1 800 g of polypropylene oxide (manufactured using polypropylene glycol as a starting material) containing 97% of allyl ether groups at the terminals and an average molecular ffi of 8000 was placed in a pressure-resistant reaction vessel equipped with a stirrer, and methyl Add 15 g of dimethoxysilane, followed by a catalyst solution of chloroplatinic acid (H2Pt C1s 6H20
8.9g, isopropyl alcohol 181g, tetrahydrofuran 160g1. solution dissolved in g) 0.34
After adding m6, the mixture was reacted at 80°C for 6 hours. As a result of regular examination of the remaining hydrosilyl groups from an IR spectrum, it was found that most of the remaining hydrosilyl groups had reacted, and a polypropylene oxide having a CH3 (CH30)2 Si -CH2CH2CH2CH20- group at the end was obtained.

Production Example 2 800 g of polypropylene oxide with an average molecular weight of aooo containing 97% of allyl ether groups at the terminals is placed in a pressure-resistant reaction vessel equipped with a stirrer, and a silicon hydride compound BOg having the following structure is added, followed by chlorination. Platinic acid' catalyst solution (same as Production Example 1) 0.34m+
, d were added and reacted at 80°C for 6 hours.

As a result of IR analysis, there was no residual hydrosilyl group, and there was no residual hydrosilyl group at the end. Polypropylene oxide with groups was changed.

Examples 1 to 4 1.0 g of the polymer obtained in Production Example 1 was added to 100 g of toluene.
g, and then dibutyltin diacetylacetonate o, osg were added to prepare a stripping agent solution.

The obtained release agent solution was applied to a 25J thick polyester film (trade name: Nilmirror Film #25, manufactured by Bunshita ■).
The coating amount after drying is 0.3 (1/+
112.0.7g 7m 2.1.0g/m2.2.0
g/m 2 and heat-treated at 90° C. for 1 minute to produce four types of releasable films.

Rubber adhesive craft tape (
Product name: Sekisui Craft Table, manufactured by Sekisui Chemical Co., Ltd.
The adhesive force was 330 Mcl), and the peeling force was measured after bonding by reciprocating twice with a 2 Jl rubber roll.

In addition, in order to check the writability of the resulting removable film, I tried writing with a commercially available oil-based pen (product name: Magic Ink M 500), but in both cases I was able to write clearly without repelling the ink. The results were summarized as
Shown in the table.

Comparative Examples 1 to 3 A commercially available long-chain alkyl pendant type release agent (trade name: B-Roil 1010, manufactured by Ippo Sha Yushi Kogyo ■) was applied in the same manner as in Example 1 (Comparative Example 1), a commercially available silicone release agent Example 1 and Comparative Example 2) where a molding agent (product name: '/3 R3022, Toshiba Silicone @1lJ) was applied in the same manner as Example 1, and an untreated one (Comparative Example 3). Similar measurements were made. The results are shown in Table 1.

[Left below] From the results in Table 1, the results using the release agent of the present invention were as follows:
It can be seen that it has both good releasability and writability.

Example 5 Polymer 1.01) obtained in Production Example 2 was mixed with toluene 10
0Q, then dibutyltin dilaurate o, os
g was added to prepare a release agent solution.

The obtained release agent solution was applied onto Lumirror Film #25 so that the coated layer after drying was 0.7 o /ra 2 and heated at 100° C. for 1 minute to produce a release film.

The writability of the obtained releasable film, which was measured in the same manner as in Example 1, was as good as in Example 1.

Rubber-based adhesive craft tape was pasted on the resulting releasable film by moving a 2ka rubber roll back and forth twice, and heated at 65°C.
After being left in an atmosphere of 80% RH for 3, 5, and 12 days, the tape was taken out, returned to air temperature, and the peeling force, tack, adhesive force, and residual adhesion rate of the peeled adhesive tape were measured.

The results are shown in Table 2.

Margin below C] From the results in Table 2, it can be seen that the products using the release agent of the present invention have excellent release performance not only at the initial stage but also after the 65°C x 80% R)-1 treatment, and are durable. It can be seen that this has almost no negative effect on the adhesive performance of the adhesive tape.

[Effects of the Invention] When a releasable film is produced using the release treatment agent of the present invention, a releasable film having both releasability and secondary properties can be obtained.

('74-

Claims (1)

[Claims] 1 The main chain is essentially represented by the general formula: -R^1-O- (wherein R^1 represents a divalent hydrocarbon group having 1 to 8 carbon atoms) 1. A peeling treatment agent comprising an alkylene oxide polymer having a molecular weight of 300 to 30,000 and having at least one reactive silicone functional group in the molecule.